The present invention relates to self-protonated sulfonic acid-substituted polyaniline compositions, ammonium salts thereof, their derivatives, processes for their preparation, and uses thereof.
Polyaniline is a family of polymers that has been under intensive study recently because the electronic and optical properties of the polymers can be modified through variations of either the number of protons, the number of electrons, or both. The polyaniline polymer can occur in several general forms including the so-called reduced form (leucoemeraldine base), possessing the general formula ##STR1## the partially oxidized so-called emeraldine base form, of the general formula ##STR2## and the fully oxidized so-called pernigraniline form, of the general formula ##STR3##
In practice, polyaniline generally exists as a mixture of the several forms with a general formula (I) of ##STR4##
When 0.ltoreq.y.ltoreq.1, the polyaniline polymers are referred to as poly(paraphenyleneamineimines) in which the oxidation state of the polymer continuously increases with decreasing value of y. The fully reduced poly(paraphenyleneamine) is referred to as leucoemeraldine, having the repeating units indicated above corresponding to a value of y=1. The fully oxidized poly(paraphenyleneimine) is referred to as pernigraniline, of repeat unit shown above corresponds to a value of y=0. The partly oxidized poly(paraphenyleneamineimine) with y in the range of greater than or equal to 0.35 and less than or equal to 0.65 is termed emeraldine, though the name emeraldine is often focused on y equal to or approximately 0.5 composition. Thus, the terms "leucoemeraldine", "emeraldine" and "pernigraniline" refer to different oxidation states of polyaniline. Each oxidation state can exist in the form of its base or in its protonated form (salt) by treatment of the base with an acid.
The use of the terms "protonated" and "partially protonated" herein includes, but is not limited to, the addition of hydrogen ions to the polymer by, for example, a protonic acid, such as mineral and/or organic acids. The use of the terms "protonated" and "partially protonated" herein also includes pseudoprotonation, wherein there is introduced into the polymer a cation such as, but not limited to, a metal ion, M.sup.+. For example, "50%" protonation of emeraldine leads formally to a composition of the formula ##STR5## which may be rewritten as ##STR6##
Formally, the degree of protonation may vary from a ratio of [H.sup.+ ]/[--N.dbd.]=0 to a ratio of [H.sup.+ ]/[--N.dbd.]=1. Protonation or partial protonation at the amine (--NH--) sites may also occur.
The electrical and optical properties of the polyaniline polymers vary with the different oxidation states and the different forms. For example, the leucoemeraldine base, emeraldine base and pernigraniline base forms of the polymer are electrically insulating while the emeraldine salt (protonated) form of the polymer is conductive. Protonation of emeraldine base by aqueous HCl (1M HCl) to produce the corresponding salt brings about an increase in electrical conductivity of approximately 10.sup.12 ; deprotonation occurs reversibly in aqueous base or upon exposure to vapor of, for example, ammonia. The emeraldine salt form can also be achieved by electrochemical oxidation of the leucoemeraldine base polymer or electrochemical reduction of the pernigraniline base polymer in the presence of an electrolyte of the appropriate pH. The rate of the electrochemical reversibility is very rapid; solid polyaniline can be switched between conducting, protonated and nonconducting states at a rate of approximately 10.sup.5 Hz for electrolytes in solution and even faster with solid electrolytes. (E. Paul, et al., J. Phys. Chem. 1985, 89, 1441-1447). The rate of electrochemical reversibility is also controlled by the thickness of the film, thin films exhibiting a faster rate than thick films. Polyaniline can then be switched from insulating to conducting form as a function of protonation level (controlled by ion insertion) and oxidation state (controlled by electrochemical potential). Thus, in contrast to, other polymeric materials for example, polypyrrole, polyaniline can be turned "on" by either a negative or a positive shift of the electrochemical potential, because polyaniline films are essentially insulating at sufficiently negative (approximately 0.00 V vs. SCE) or positive (+0.7 V vs. SCE) electrochemical potentials. Polyaniline can also then be turned "off" by an opposite shift of the electrochemical potential.
The conductivity of polyaniline is known to span 12 orders of magnitude and to be sensitive to pH and other chemical parameters. It is well-known that the resistance of films of both the emeraldine base and 50% protonated emeraldine hydrochloride polymer decrease by a factor of approximately 3 to 4 when exposed to water vapor. The resistance increases only very slowly on removing the water vapor under dynamic vacuum. The polyaniline polymer exhibits conductivities of approximately 1 to 20 Siemens per centimeter (S/cm) when approximately half of its nitrogen atoms are protonated. Electrically conductive polyaniline salts, such as fully protonated emeraldine salt [(--C.sub.6 H.sub.4 --NH--C.sub.6 H.sub.4 --NH.sup.+)--Cl.sup.- ].sub.x, have high conductivity (10.sup.-4 to 10.sup.+2 S/cm) and high dielectric constants (20 to 200) and have a dielectric loss tangent of from below 10.sup.-3 to approximately 10.sup.1. Dielectric loss values are obtained in the prior art by, for example, carbon filled polymers, but these losses are not as large nor as readily controlled as those observed for polyaniline.
The present invention is related to the invention disclosed in the parent co-pending application Ser. No. 07/423,902 filed Oct. 19, 1989 now U.S. Pat. No. 5,137,991 which is a continuation-in-part application of Ser. No. 193,694 filed May 13, 1988 now U.S. Pat. No. 5,079,334 which are expressly incorporated herein by reference. The Ser. No. 07/423,902 filed Oct. 18, 1989, U.S. Pat. No. 5,137,991 application discloses self-protonated sulfonic acid-substituted polyaniline compositions, their derivatives, processes for their preparation and various uses thereof.
The present invention also relates to the co-pending patent application Ser. No. 07/426,959 filed Oct. 24, 1989 now U.S. Pat. No. 5,164,465 which is expressly incorporated herein by reference. The application Ser. No. 07/426,959 filed Oct. 24, 1989, now U.S. Pat. No. 5,164,465 is a continuation-in-part of the Ser. No. 07/423,902 filed Oct. 19, 1989, now U.S. Pat. No. 5,137,991 and discloses non-protonated sulfonated polyaniline salt compositions which are electrically insulating polymers and which readily dissolve in aqueous solutions.
While the preparation of polyaniline polymers and the protonated derivatives thereof is known in the art, it is novel to prepare sulfonated polyaniline compositions which are capable of being "self-protonated" or "self-doped". The use of the terms "self-protonated" and "self-doped" herein includes, but is not limited to, the reorganizaton of hydrogen ions on the polymer i.e., the absence of any counterion not covalently bonded to the polymer chain. For example, self-doping or self-protonation of a polyaniline base polymer leads to a polyaniline salt polymer and a reorganization of the electronic structure which then forms a polaronic metal. The conductivity of such polaronic metal is independent of external protonation.
However, there is a need for facile methods for processing and using the sulfonated polyaniline compositions and ammonium salts thereof. Such methods will aid in the commercial development of useful conducting sulfonated polyaniline compositions and their derivatives.